碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应

锌空气电池(ZABs)具有高能量密度(1086 mWh gZn^(–1))、价低、易回收等优势,引起了学者们的广泛关注.空气电极发生的氧还原反应(ORR)/氧析出反应(OER)是控制整个ZABs效率的关键.因此,设计和开发高效的ORR电催化剂对于ZABs商业化至关重要.目前,Pt基电催化剂仍是最有效的ORR电催化剂,但Pt资源稀缺,价格高昂,Pt基电催化剂稳定性差等缺点阻碍了其商业化.因此,研究高活性和高稳定性的ORR非贵金属电催化剂十分重要.碳点(CDs)作为一种新型的零维高分子碳材料,具有低毒、高导电性等优势,被广泛用于碳基材料的前驱体.CDs具有sp^(2)杂化晶核、丰富的边缘位点和大量的官能团(如‒NH_(2),‒COOH和‒OH),这些表面官能团为过渡金属原子提供了很强的锚定位点,可用于构筑各种碳负载过渡金属催化剂.本文设计合成了一种新型的碳基ORR电催化剂,其由CDs衍生的三维碳纳米花(CNF)负载Co单原子(SAs)和纳米颗粒(NPs)构成.利用CDs在二次水热过程中形成了3.66 nm的超薄纳米膜并构筑成3D的多孔CNF结构.X射线衍射、高角度环形暗场原子分辨率扫描跃迁电子显微镜和X射线吸收光谱结果表明,材料中的SAs和NPs共存.测试结果表明,Co SAs/NPs CNF拥有可以和商业Pt/C相当的ORR活性(E_(1/2)=0.83 V(vs.RHE),j_(L)=6.13 mA cm^(-2)),且具有良好的稳定性.同时,利用SCN–可以毒化SAs和NPs,而EDTA只能毒化SAs的特性,证明了Co SAs和Co NPs协同促进了整个催化反应过程.理论计算表明,相邻Co NPs的存在优化了Co-N_(4)位点的电子结构,显著降低了ORR决速步骤(*OOH吸附)的能垒.因此,在整个催化反应过程中,Co SAs和Co NPs协同改善了ORR过程中的电子和质子转移行为.Co SAs/NPs CNF较大的比表面积和丰富的多孔结构有利于O_(2)和质子传输,基于其组装的ZABs的能量密度高达1000.58 mWh gZn^(–1)(理论值的93.69%)和循环运行1300次性能依然稳定.综上,本工作为高性能ORR电催化剂的设计提供依据.

A novel P-doped and NCDs loaded g-C_(3)N_(4) with enhanced charges separation for photocatalytic hydrogen evolution

Graphite carbon nitride(g-C_(3)N_(4)) is a promising non-metal photocatalyst for photocatalytic hydrogen production, but its performance is still limited due to sluggish charges separation and low utilization of light.In this work, P-doped and N-doped carbon dots(NCDs) supported g-C_(3)N_(4)were successfully prepared via hydrothermal and polymerization reactions. The sub-bandgap formed by P-doping enhances the utilization of visible light, and the high electron density of P sites is conducive to the trapping of holes. NCDs also improve light utilization and, more importantly, act as electron acceptors and transporters to promote electron transport. The built-in electric field formed by the synergy of P-doping and NCDs-loading greatly promotes the separation of charges. The PCN/NCDs showed a significantly improved hydrogen evolution activity of 3731 μmol h^(-1)g^(-1), which was 6.7 times that of pure carbon nitride(560 μmol h^(-1)g^(-1)). This strategy may be generalized to the design of g-C_(3)N_(4)-based photocatalysts, facilitating the separation of charges for enhanced catalytic activity.

Synthesis of Al_2O_3-SiC Composite and Its Effect on the Properties of Low-carbon MgO-C Refractories

Al2O3-SiC composite was synthesized with pyrophyllite and natural graphite as raw materials by carbothermal reduction reaction under argon atmosphere. The effect of synthesis temperature on phase composition and microstructure was investigated. Low-carbon MgO-C refractories were prepared by using the synthesized Al2O3-SiC composite as additive. The effect of its addition on the slag penetration and corrosion resistance as well as oxidation resistance of the refractories was investigated, and the slag resistance and oxidation resistance mechanisms of the Al2O3-SiC composite were also discussed. The results show that the synthesis temperature has a great influence on preparation of Al2O3-SiC composite. The Al2O3-SiC composite can be synthesized at 1873-1973 K under argon atmosphere, with pyrophyllite and natural graphite as raw materials, and particle sizes of the composite synthesized at 1973 K are mainly distributed as 1-2 μm. The slag penetration and corrosion resistance of low-carbon M80-C refractories can be remarkably improved by adding the synthesized Al2O3-SiC composite, and the oxidation resistance has an improvement to some extent. The increase of slag viscosity and the formation of MgAl2O4 can effectively inhibit the slag penetration and corrosion for the refractories.

非共轭分子衍生的红色发射碳点的光致发光机制探究

在碳点基发光材料中,红光和近红外波长发射性质的开发一直是目前研究的热点和难点,其在生物学领域和显示领域等具有广阔的应用前景;然而,红光碳点的形成过程和荧光机理均不明确,这使得高品质红光碳点的制备依然面临巨大挑战.针对上述难题,作者提出氮(N)诱导芳构化的策略,精准调控碳点中五元芳环和六元芳环的形成过程,并通过高分辨制质谱结合密度泛函理论计算深度解析了柠檬酸基红光碳点的荧光发射中心.作者选取柠檬酸和一系列类柠檬酸分子,如乌头酸、酒石酸、天冬氨酸、苹果酸和顺丁烯二酸等作为反应前驱体进行探究,结果表明,柠檬酸类似物种碳链长度的不同会影响所制备碳点的荧光发射波长,前体碳链长度会影响N参与的扣环形式,从而导致不同程度的红移.其中,柠檬酸基碳点可形成N掺杂六元芳环,从而实现荧光发射波长从无N掺杂的423 nm到有N掺杂的667 nm,高达244 nm的大幅度红移.本工作揭示了柠檬酸或类柠檬酸等非共轭小分子为碳源制备红光碳点的生长过程和其荧光发射中心,并为其他类型碳点的荧光机制探索和结构分析提供了创新思路.

Electron-phonon coupling-assisted universal red luminescence of o-phenylenediamine-based carbon dots

Due to the complex core-shell structure and variety of surface functional groups,the photoluminescence(PL)mechanism of carbon dots(CDs)remain unclear.o-Phenylenediamine(oPD),as one of the most common precursors for preparing red emissive CDs,has been extensively studied.Interestingly,most of the red emission CDs based on oPD have similar PL emission characteristics.Herein,we prepared six different oPD-based CDs and found that they had almost the same PL emission and absorption spectra after purifiication.Structural and spectral characterization indicated that they had similar carbon core structures but diffferent surface polymer shells.Furthermore,single-molecule PL spectroscopy confirmed that the multi-modal emission of those CDs originated from the transitions of different vibrational energy levels of the same PL center in the carbon core.In addition,the phenomenon of"spectral splitting"of single-particle CDs was observed at low temperature,which confirmed these oPD-based CDs were unique materials with properties of both organic molecules and quantum dots.Finally,theoretical calculations revealed their potential polymerization mode and carbon core structure.Moreover,we proposed the PL mechanism of red-emitting CDs based on oPD precursors;that is,the carbon core regulates the PL emission,and the polymer shell regulates the PL intensity.Our work resolves the controversy on the PL mechanism of oPD-based red CDs.These findings provide a general guide for the mechanism exploration and structural analysis of other types of CDs.

Single stain hyperspectral imaging for accurate fungal pathogens identification and quantification

The most widely used method of identification of microbial morphology and structure is microscopy,but it can be difficult to distinguish between pathogens with a similar appearance.Existing fluorescent staining methods require a combination of a variety of fluorescent materials to meet this demand.In this study,unique concentration-dependent fluorescent carbon dots(CDs)were synthesized for the identification and quantification of pathogens.The emission wavelength of the CDs could be tuned spanning the full visible region by virtue of aggregation-induced narrowing of bandgaps.This tunable emission wavelength of the specific concentration response to diverse microbes can be used to distinguish microorganisms with a similar appearance,even in a same genus.A hyperspectral microscopy system was demonstrated to distinguish Aspergillus flavus and A.fumigatus based on the results above.The identification accuracy of the two similar-looking pathogens can be close to 100%,and the relative proportions and spatial distributions can also be profiled from the mixture of the pathogens.This technique can provide a solution to the fast detection of microorganisms and is potentially applicable to a wide range of problems in areas such as healthcare,food preparation,biotechnology,and health emergency.

Cross-linking enhanced room-temperature phosphorescence of carbon dots

Currently,there is a strong drive to discover alternative materials that exhibit room-temperature phosphorescence(RTP)for displays,bioimaging,and data security.Ideally,these materials should be nontoxic,cheap,and possess controllable photoluminescent properties.Carbon dots(CDs)possess each of these characteristics,but to date,less attention has been paid to their RTP mechanism.Herein,we synthesized a series of CDs by self-crosslinking and carbonization of precursor.The resultant CDs were luminescent and exhibited a bright,micro-second afterglow lifetime.To increase the RTP,a second microwave processing step was used to coat the CDs with polyvinyl alcohol(PVA),polyacrylamide(PAM),or tetraethyl orthosilicate(TEOS),producing CDs@PVA,CDs@PAM,and CDs@TEOS composites.The core-shell structure acted to enhance crosslinking at the surface of the CDs to boost the RTP,creating abundant energy levels for intersystem crossover.In situ X-ray photoelectron spectroscopy verified electron transfer during luminescence.Finally,we present a design rule that can be used to tune the quantum yields and RTP lifetime of CDs,based on the effective stabilization of triplet excited states through the extent and strength of cross-linking.This simple strategy provides a flexible route for guiding the further development of CDs with tailored RTP properties for various applications.